Hydrocarbon conversion process with the use of a grainy silicaalumina type catalyst



Patented Apr. 17, 1951 UNITED STATES PATE T OFFICE HYDROCARBON CONVERSION PROCESS WITH THE USE OF A GRAINY SILICA- ALUMINA TYPE CATALYST George R. Bond, Jr., Paulsboro, N. J assignor to Houdry Process Corporation, Wilmington, Del., a corporation of Delaware No Drawing. Application December 26, 1947, Serial No. 794,128

7 Claims.

The present invention relates to the catalytic conversion of hydrocarbons such as fractions obtained or derived from petroleum or other carbonaceous or hydrocarbonaceous materials, and is particularly concerned with such conversion processes in which cracking catalysts can be employed, as for instance in promotingscission of carbon to carbon linkages or in the typical reactions occurring in the reformation of liquid products boiling in the range of gasoline and naphthas.

cially employed in hydrocarbon conversion processes of the type designated include certain clays in natural or processed state, such as acid-activated montmorilloniteclays, and certain synthetic gel composites such as those of silica with a catalytically active metal oxide, for example alumina, zirconia, magnesia, beryllia, etc. known are siliceous plural oxide gel catalysts containing several of these metal oxides or one or more of these oxides and an additional metal oxide, stated to serve as a promoter or the like or to confer special properties. In commercial operations, particularly in cracking of higher.

boiling hydrocarbons for the production of'gasoline, catalysts comprising silica and alumina have been most generally employed.

In the preparation of synthetic siliceous catalysts, a number of diverse methods are disclosed.

encountered in washing and purifying these I products, particularly in their wet hydrogel' state. The synerised hydrogel still contains considerable'quantities of water which is required to be removed 'for production of the desired dry gel product. The formation of the dried gel or the hydrogel into bodies of desired sizes and shapes,

as is required for catalysts used in certain hydrocarbon conversion systems, is not readily accomplished by simple methods such as extrusion and therefore special procedures and apparatus for forming, casting, or molding must generally be Known catalysts proposed for use or commere employed. These expensive operations'it will be seen, considerably increase the cost of synthetic catalyst manufacture. i

In my copending application Serial No. 794,129,

filed of even date herewith, certain simple, ef-

ficient and more economical methods of prepar ing plural oxide siliceous catalysts are described,

' whereby non-gelatinous precipitates of initially Also low water content are obtained as reaction products, which can be directly formed, if desired, into agglomerated bodies of required size and shape.

The obtained non-gelatinous products do not require precise handling in drying to avoid detrimentalstructural changes and impairment of catalytic activity, as do products of the gel type.

Besides the advantages in methods of preparation, the obtained granular products demonstate important advantges in properties as compared with synthetic gel catalysts, when employed in hydrocarbon conversion processes, including decreased coke and gas formation for a given 'con-. version of higher boiling hydrocarbons to gaso-- line. Thus, in accordance. with the present invention, hydrocarbonconversion processes of the type employing cracking catalysts are advantaggeously improved by the use of these dried nongelatinous precipitates comprising silica and a catalytically active metal oxide, such asalumina, obtaining high or acceptable yields of desired liquid conversion-products,with the concomitant 7 formation of smaller quantities; of by-products such as coke andgas. properties of these novel catalysts renders the same particularly of importantadvantage in cracking lessrefractory tocks which character-.

istically have a tendency to produce comparatiyey g ly large'quantities of coke.

' The novel catalysts areprepared by the meta ods described in mycopending application referred to or as hereinafter described. Generally, the preparation involves reacting compounds yieldin the desired catalytic components,,in high concentrations and in the absence of large quantities of liquid medium, to produce a nongelatinous precipitate, of a generally granular nature. The-obtained precipitate, because of its non-gelatinous character, can be readily further processed as required, as by Washing or other purification treatment, since the wash liquids are readily separated and removed. Because .of the comparatively low liquid content of the obtained granular precipitate, it can be dried in a relatively short time, and without necessitating the precise precautions other-wise required .in drying products of the gel type to avoid detrimental.

The typical low coking;

changes in structure and accompanying impairment of catalyst activity. The granular product, moreover, can be directly formed into agglomerated bodies of desired size and shape by simple and rapid methods, such as ordinary casting or extrusion.

In order to obtain the desired reaction products of the invention, it is necessary that the product concentration of the components forming the ultimate catalyst, in the liquid reaction medium, be not less than about 150 grams of such components per liter of total reaction mass. At the lowest indicated product concentration, the reaction mass will be at least a highly viscous liquid and with increasing product concentrations may range from a stifi paste to an almost dry appearing mass.

Catalysts of higher activity level are frequently obtained at higher product concentrations, as in excess of 250 grams of catalytic oxides per liter of total reaction mass.

The reasons for the improved catalytic behavior of these granular catalysts cannot be easily explained. Without being bound to any particular theory as to this favorable behavior of the present catalysts, it is believed that the same may be due in part to the pronounced heterogeneity of the catalyst surface as opposed to the greater homogeneity of catalysts of the gel type: discreet particles of S102 and A1203, etc, lying side by side instead of being more intimately associated, possibly as a definite aluminum silicate, as in the gel type. By virtue of this heterogeneity, innumerable active spots may develop on the surface of the catalyst, capable of undergoing momentary large temperature fluctuations favorable to the breaking down of the hydrocarbon molecules to fractions lying in the gasoline boiling range while minimizing the more severe cracking to gas and coke which is characteristic of gel type catalysts, believed to be due to the greater adsorptivity of the latter by virute of their extensive'capillary structure.

For the preparation of the improved siliceous catalysts, the silica component may be precipitated from any silicate having appreciable solubility in aqueous media, including crystalline silicates, such as sodium metasilicate, commercial solutions of water glass of various siOz/NazO ratios, or solutions of alkali metal metasilicates.

The other metal oxide or oxides of the ultimate catalyst maybe any of those known or heretofore employed in catalysts of this type. including non-reducible metal oxides and particularly oxides of amphoteric metals; such as alumina,

zirconia, magnesia, beryllia, etc, or combinations of these.

reaction medium will be necessary. On the other hand, if water or other liquid is not released or provided by the reactants employed, it will e necessary to supply a small amount of water to facilitate good mixing and to further the reaction. In such instance, the water may be supplied by previously dissolving or. wetting any one or more of the reactants, or the water may be added to the admixture of the reactants.

With the drier or more highly concentrated compositions employed in the reaction to effect precipitation, where migrations of reacting ions may be quite slow, more intimate contact be tween the reactants, can be obtained by stirring and grinding these together. as in a mortar, edgerunner, or ball mill.

The same considerations as to the ratio of silica to the other metal oxides that applyto the known siliceous gel type catalysts are also generally applicable in the case of the catalysts of the invention; the silica component of the plural oxide catalyst predominating. Thus in the preparation of silica-alumina catalysts, weight ratios of from about 95/5 to 55/45 silica to alumina may be employed to produce catalysts of acceptable physical and performance properties.

The reactants should be selected and the reaction conditions adjusted so that reaction takes place under conditions maintaining a pH of from about 2 to 10 and preferably about 4 to 9. Although highly active catalysts can be prepared by the described method at pH below 4, the solubility of amphoteric metal oxides in this range requires more precise handling. The non-' siliceous reactant should advantageously be selected so as to provide easily removable anions.

The desired pH range is obtained by employing an alkali metal silicate furnishing alkali in zation. Once reaction in high product concentration has been substantially completed, the reaction mass may be diluted by addition of liquid, if desired, without adversely affecting the granular nature of the precipitate.

Example I A solution of commercial water glass of 1.40

specific gravity having the approximate composition NazO-3.33Si0z (N-Brand) was thoroughly admixed mechanically with powdered sodium aluminate to furnish a theoretical weight ratio of parts SiOz to 10 parts A120: (1262 parts of water glass solution to '77 parts of sodium aluminate).

Concentrated sulfuric acid was diluted with water furnishing a mixture containing 216 parts of H250; and 276 parts H2O, which acid mixture was added to the previous mixture of silicate and aluminate and the entire slurry whipped for several minutes. The slurry had a product concentration of 310 grams SiOz and A1203 per liter and was of 3 pH.

The slurry was warm due to exothermic reaction and showed the presence of some unprecipitated aluminum ion. The slurry was diluted with 1000 parts by weight of water, to reduce viscosity and permit ready stirring and uniform admixture of ammonium hydroxide added to bring the pH of the slurry to 4.5. The ammonia treated slurry filtered readily and extremely rapidly, and left a residual granular precipitate.

The obtained precipitate was washed with distilled water until free of sulfate then washed with ammonium chloride solution a number of times and again with water until chloride free. The wash solutions separated quite easily and rapidly.

asessco:

i A. portionof the washed" product-was dried). AA and :regrouncl. and 1 admixed-. with -thevremainder of the wet mass. to form a mass of mold: able consistency.- This mass. was cast into pellets .of- 4 mmpsize and the pellets drieda Drying of 1 the pellets. was accomplished without appreciable shrinkagein contrast tothe high degree of shrinkage characteristic of angel; The dried pellets were. quite firm 'andhad. an sapparent density of. 0.38.,(measured asl kgmprpert-m liter of packed pellets):.:

Example II The same general procedure was followed as in the preceding example to obtain a theoretical weight ratio of 90SiO2/10A12O3, but the reactants admixed in' concentrations furnishing 333 grams SiO2.Al2Ox-..-per .liter of total,..slurry. 'IheAN-Br'and. silicate was ground together with the powdered sodium aluminate in propor- 2n tions of 631 parts'by weight silicate solution to 38:5 partsof the .aluminate. An aqueous solu= tion.;of sulfuric acid and ammonium sulfate was then: prepared containing: per liter of: solution" 482igrams H2804 and 218 grams ammonium sul- 2,

fate, (NH4)2SO4 dissolved therein. Anamount of the thus prepared acid solution furnishing I the S04 equivalent of the NagO content of the. mix, was added tothe ground mass. Stirring was continued during reaction, which resulted in the formation of a grainy paste of 7 pH.'

After removal of water; by filtering and purification of the product astin' the preceding example, a portion of the wet,"washed and filtered product was extruded into pellets and dried. No'

appreciable shrinkage occurred on drying.

Another portion of the'washed product was thoroughly mixed and filtered to remove excess water then about one-third'of the mass dried in an oven. The dried product was ground .to 100" mesh and remixed with the wet portion, and the obtained mix cast into pellets- The resulting pellets were quite hard and had an apparent density of 0.42.

Example III 4 An aqueous hydrochloric acid solution containing 131 parts by weight HCl and 369 parts H2O was admixed with 95 parts crystalline a1u.-. minum chloride, A1Cl3.6H2O (furnishing 20 parts:

A1203), and with 64 parts ammonium chloride. 5

The mixture was stirred with heating and additional water added to effect complete solutionof the chlorides.

The acid chloride solution was then added to 637 parts sodium metasilicate (furnishingz5l80 parts SiOz) and the batch ground in a mortar until reaction was complete. Product concentration of SlO2.A12O3=182 grams/liter; pH of batch=7. The reaction mass was filtered easily, leaving a grainy precipitate.

'I'heobtainedxprecipitatewas washed with-distilledwateruntil substantially free of SOr'ions, then". with 5% ammoniumchloride-solution;

Odor'of ammonia was noted at the start-of the Q1 ammonium chloride wash indicating that: some of the metasilicate had. not reacted." The mass extruded easily without much shrinkage on drying..

Afterthe finaliwash, the mass was filtered to' 1 removeexcess liquid andcast directly 'intopel lets and dried. The drid pellets were iairly-hard u and had an apparent density of 0.40.

Example IV Commercial water glass solution N-Brand f) I and sodium aluminate were ground together in a mortar; and-an aqueous gsolutionyoi ammonium chlorideand hydrochloric acidadded theretonto; furnish Clions equivalent to the NazO contentz y giving-the following: proportions. -by weight Water-glass-s-olution 634;0 Sodium aluminate -s 3&5 I-I 61.5 NHiCl 30.2

Water sufiicient; to givea product concentration of 286, grams A12O3.Si02 per liter.

SiOz/AlzOs weight ratio 9/1 pH of batch 7.5

the above examples, other silica-alumina cast pellets were-prepared at variouspI-I anddifierent product concentrations, including:

Ezrample V A batch of 276 grams, per literSiGaAlzOa of-.9.5

pH and 9/1 silica to .alumina ratio prepared from commercial 'sili'catesolution. (N Brand -i), s01. dium alu'minate and. ammonium sulfate;

Example VI One of 273 gramsper liter and 9 pH prepared from the same reactants with a 75/25 silicato alumina'ratio;

No" diificulty" was encountered in treating, washing, or pelletingany of these batches.

Ezcatmple- VII A solution of commercial zirconium sulfate (zircotan) was employed containing per literhof solution. 141.3 .grams of Z1 02 and 402 grams S04. To a quantity of thissolution furnishing 50 parts by -weight 2102 there was added- 75:8 parts-by" weight *commercial concentrated sulfuric acid H2804) and to the admixed solutions there was then''added= 1,585 parts by weight of commer-- cial water glass, N-Brand, of TAO-specific grav a-i ity, providing 450 parts by weightSiOz giving a These proportions: .resulted in the production of a s1urry having .a

product concentration of :ZrOz plus SiOz' of. 328 grams per liter of slurry.

Thisslurry, which .wasfound to have .a pH- of" 2.5, was then adjusted to pH 5 by =addition--of--;

concentrated ammonium hydroxide and the re-:

sulting product then thoroughly incorporated in a wet mill to form a homogeneouspasty mass.;-: 1 The milled mass was easily filtered,-then-washed j with water until sulfate free, then with diluteaame monium chloride solution for removal of-yalkalig metal ions, and finally again with water untiltj chloride free. Thewash liquor drained readily...

The 'obtainedpurified (grainy pastei-was .castiintoe? 4 mm. pellets'and the pellets dried.

The .catalytic activity of pelleted. catalyst :pre-w pared as described in theforegoing examples was; tested. bythe CAT-A? methodi-described-;by..a 1

Alexander and H. G. Shimp in National Petro- F., 90% at 889 F.). The gas oil was cracked at an average bed temperature of 875 F., at a space rate of 1 (vol. liquid charge/per vol. catalyst/per hr.) under a pressure of 10 pounds per square inch gauge, 10% by weight of steam being added to the charge, over an on-stream operating period of ten minutes. The yields obtained are shown in Table 2 below.

The same gas oil as above was also cracked with other catalysts of the examples, heat treated as indicated, obtaining yields shown in Table 2.

Table 2 Yields Catalyst Heat Treat Liquid Converv l u gi 35:12: wfiil ilt Gas ,291,2 Per cent Per cent Per cent Grav' Example I. 1250 F., 4 hrs. 100% 1120.. 98. 3 39. 7 37. 9 l. 2 6. 4 -L 50 Example II. 1400 F., hrs, 5% H 89. 8 60. 0 49. 8 3. 4 14.0 1.55 Example III. do 96. 9 39. 0 35.9 1. 5 6. 9 140 Example V do 97. 2 43. 8 41. 0 1. 6 8. 1 1. 48 Example VI rlo i 95 2 6 41. 8 l. 6 8. 9 1. 37 Example VII do -I 89. 7 66 4 56.0 4. 0 l3. 7 '1.

the catalyst. In addition, the quantity of carbonaceous deposit formed in the catalyst is also usually measured and expressed in terms of It will be noted that the catalyst of Example I gave a gasoline/coke ratio of over 31, and even at the high degree of conversion with the more weight percent of charge, and the specific gravity active catalyst of Example II (CAT-A=38.1% and weight percent of gas produced is also degaso. the quantity of coke and gas formed is termined. surprisingly 10w; typical commercial synthetic Previous to testing, the pellets were calcined to silica-alumina gel catalyst at substantially the stabilized activity by treating the same in 95% same conversion level with this charge stock will air and 5% steam (volumes) at 1400 F. for 10 35 produce in the order of about 5% by weight coke hours. The average activity of typical catalysts and about 20% by weight gas. of the invention is shown in the following tabula- The catalysts of the invention can be employed tion. in cracking of light or heavy hydrocarbons as To determine their steam stability, certain of well as in the catalytic treatment of gasoline the catalysts were also treated in 100% steam for and naphthas under cracking conditions to imfour hours at 1250 F. and then tested for crackprove their quality (reforming). In systems eming activity with results shown in the table below: ploying a fixed catalyst bed or moving solid bed Table 1 CAT-A Yields H t Catalyst with Gas0., Coke, Gas, Gas Gaso./

V Weight Weight coke, Per Cent Per Cent Per Cent Ratio 2-2 is at Example II 3 L1 g 2% 327% Example III 3 g 1. g g

Example lg 7 $3 0 1:39 3241 Example vn. 35. 5 1. 5 a 5 1. 43 23. 7 1

(a) 95% air, 5% H2O10 hrs.-l400 F.

(b) 100% Hlo4 hrs.1250 r.

The excellent gasoline/coke and gasoline/gas of catalyst, the catalyst is advantageously em ratiosdisplayed by these catalysts at the indiployed'in the form of aggregates such as pellets, cated activity levels renders these of particular coarse granules, tablets or the like, and the advantage for use in cracking of oils charactergreater facility of forming such aggregates from istically yielding comparatively large quantities precipitates prepared in accordance with the in- The catalyst of Example I after treatment with steam for 4 hours at 1250 F. (CAT-A activity 24.3% gasoline) 'was employed in cracking a heavy gas oil; an East Texas gas oil fraction of 29.0" API gravity and boiling over the range (VA) vention is one of the important advantages obtained. For use in other known systems of hydrocarbon conversion, as where the catalyst is suspended in a fluid medium, smaller particles or more finely divided catalyst is preferred, in which event the forming or casting step need not be practiced and the precipitated product may be broken up or ground to desired size and then dried; or larger dried aggregates can be comof 530 initial to 95% at 930 F. (50% at 746 minuted to required size.

In the use of the catalysts according to the present invention no change in usual conditions of treatment of the hydrocarbon to be processed is rendered necessary. The usual conditions as to time, temperature, etc. can be followed if desired. As an example of a fixed bed operation, cracking may be carried out at a temperature of 800 F. to 950 F., employing a space rate (volume of charge, liquid basis, per volume of catalyst per how) of about 1.5, and a pressure of 15 pounds per square inch gauge. The temperature, of course, may be varied within the range of about 700 F. to 1100 F., the space rate within the range of about 0.5 to about 8, and pressures may be employed from about atmospheric or slightly lower up to about 100 pounds per square inch, or even higher. Under these conditions the operating period on stream may range from five to sixty minutes, for example to 30 minutes alternating with regeneration periods.

In the processes other than the fixed bed, such as where the catalyst moves through the reaction zone, the conditions employed may be such, as to subject the oil to substantially equivalent conditions including contact time and ratios of oil to catalyst as those set out above in connection with the fixed bed process. The catalyst during its cycle is passed through a separate regeneration zone.

Reforming may be carried out in accordance with the invention by charging a virgin or cracked gasoline or naphtha fraction under conditions similar to those employed in cracking. In all of these processes, the catalyst after use is regenerated by contacting it with air or other oxygen-containing gas to burn off carbonaceous deposits.

Obviously many modification and variations of the invention as hereinbefore set forth may be made without departing from the spirit and scope thereof and, therefore, only such limitations should be imposed as are indicated in the appended claims.

I claim as my invention:

1. The process of converting higher boiling hydrocarbons to gasoline by catalytic cracking which comprises contacting said hydrocarbons with a solid catalytic composition prepared by a method comprising precipitation of silica and alumina from an aqueous medium containing soluble silicon and aluminum compounds under conditions selected to form a grainy precipitate, said soluble compounds being present in said aqueous medium in such high concentrations as to furnish silica and alumina in a product concentration of at least 150 grams per liter of total reaction mass and said precipitation being effected at a pH of 2 to 10 in the presence of added acidic materials.

all

2. The process of cracking hydrocarbons which comprises subjecting the same under catalytic cracking conditions to contact with a catalyst comprising silica and alumina in a weight ratio of from about /5 to 55/45, said catalyst being a dried non-gelatinous grainy product obtained by precipitation of silica and alumina from an aqueous medium in a product concentration of at least grams silica and alumina per liter of total reaction mass and at a pH of 4 to 10.

3. The process of cracking hydrocarbons which comprises subjecting the same under catalytic cracking conditions to contact with molded pieces of catalyst prepared by a method comprising the steps of thoroughl admixing in a small quantity of liquid medium an alkali metal silicate and a salt of a metal whose oxide is catalytically active,

said alkali metal silicate and said salt being present in concentrations in said liquid medium such that the SiOz exceeds said catalytically active oxide and said SiOz and said oxide constitute at least 150 grams per liter of the total reaction mass, adjusting the hydrogen ion concentration of the reaction mass to within the range of 4 to 9 pH, by addition of acidic material, thereby forming a granular precipitate comprising silica and said oxide, washing the granular precipitate in aqueous media to remove soluble salts and base exchangeable alkali metal ions, forming the precipitate into pieces of desired size and shape, and drying said pieces.

4. The process in accordance with claim 3 wherein said catalytically active metal oxide GEORGE E. BOND, JR.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,165,578 Rembert July 11, 1939 2,315,024 Sturgeon Mar. 30, 1943 2,341,276 Kanhofer Feb. 8, 1944 

1. THE PROCESS OF CONVERTING HIGHER BOILING HYDROCARBONS TO GASOLINE BY CATALYTIC CRACKING WHICH COMPRISES CONTACTING SAID HYDROCARBONS WITH A SOLID CATALYTIC COMPOSITION PREPARED BY A METHOD COMPRISING PRECIPITATION OF SILICA AND ALUMINA FROM AN AQUEOUS MEDIUM CONTAINING SOLUBLE SILICON AND ALUMINUM COMPOUNDS UNDER CONDITIONS SELECTED TO FORM A GRAINY PRECIPITATE, SAID SOLUBLE COMPOUNDS BEING PRESENT IN SAID AQUEOUS MEDIUM IN SAID HIGH CONCENTRATIONS AS TO FURNISH SILICA AND ALUMINA IN A PRODUCT CONCENTRATION OF AT LEAST 150 GRAMS PER LITER OF TOTAL REACTION MASS AND SAID PRECIPITATION BEING EFFECTED AT A PH OF 2 TO 10 IN THE PRESENCE OF ADDED ACIDIC MATERIALS. 